Chemical vapor deposition with elevated temperature gas injection

ABSTRACT

A chemical vapor deposition reactor and method. Reactive gases, such as gases including a Group III metal source and a Group V metal source, are introduced into a rotating-disc reactor and directed downwardly onto a wafer carrier and substrates which are maintained at an elevated substrate temperature, typically above about 400° C. and normally about 700-1100° C. to deposit a compound such as a III-V semiconductor. The gases are introduced into the reactor at an inlet temperature desirably above about 75° C. and most preferably about 100°-250° C. The walls of the reactor may be at a temperature close to the inlet temperature. Use of an elevated inlet temperature allows the use of a lower rate of rotation of the wafer carrier, a higher operating pressure, lower flow rate, or some combination of these.

FIELD OF THE INVENTION

The present invention relates generally to chemical vapor depositionmethods and apparatus.

BACKGROUND OF THE INVENTION

Chemical vapor deposition involves directing one or more gasescontaining chemical species onto a surface of a substrate so that thereactive species react and form a deposit on the surface. For example,compound semiconductors can be formed by epitaxial growth of asemiconductor material on a substrate. The substrate typically is acrystalline material in the form of a disc, commonly referred to as a“wafer.” Compound semiconductors such as III-V semiconductors commonlyare formed by growing layers of the compound semiconductor on a waferusing a source of a Group III metal and a source of a group V element.In one process, sometimes referred to as a “chloride” process, the GroupIII metal is provided as a volatile halide of the metal, most commonly achlorides such as GaCl₂ whereas the Group V element is provided as ahydride of the Group V element. In another process, commonly referred toas metal organic chemical vapor deposition or “MOCVD” the chemicalspecies include one or more metal organic compounds such as alkyls ofthe Group III metals gallium, indium, and aluminum, and also include asource of a Group V element such as one or more of the hydrides of oneor more of the Group V elements, such as NH₃, AsH₃, PH₃ and hydrides ofantimony. In these processes, the gases are reacted with one another atthe surface of a wafer, such as a wafer of sapphire, Si, GaAs, InP, InAsor GaP, to form a III-V compound of the general formulaIn_(X)Ga_(Y)Al_(Z)N_(A)As_(B)P_(C)Sb_(D) where X+Y+Z=approximately 1,and A+B+C+D=approximately 1, and each of X, Y, Z, A, B, and C can bebetween 0 and 1. In some instances, bismuth may be used in place of someor all of the other Group III metals.

In either process, the wafer is maintained at an elevated temperaturewithin a reaction chamber. The reactive gases, typically in admixturewith inert carrier gases, are directed into the reaction chamber.Typically, the gases are at a relatively low temperature, as forexample, about 50-60° C. or below, when they are introduced into thereaction chamber. As the gases reach the hot wafer, their temperature,and hence their available energy for reaction, increases.

One form of apparatus which has been widely employed in chemical vapordeposition includes a disc-like wafer carrier mounted within thereaction chamber for rotation about a vertical axis. The wafers are heldin the carrier so that surfaces of the wafers face upwardly within thechamber. While the carrier is rotated about the axis, the reaction gasesare introduced into the chamber from a flow inlet element above thecarrier. The flowing gases pass downwardly toward the carrier andwafers, desirably in a laminar plug flow. As the gases approach therotating carrier, viscous drag impels them into rotation around theaxis, so that in a boundary region near the surface of the carrier, thegases flow around the axis and outwardly toward the periphery of thecarrier. As the gases flow over the outer edge of the carrier, they flowdownwardly toward exhaust ports disposed below the carrier. Mostcommonly, this process is performed with a succession of different gascompositions and, in some cases, different wafer temperatures, todeposit plural layers of semiconductor having differing compositions asrequired to form a desired semiconductor device. Merely by way ofexample, in formation of light emitting diodes (“LEDs”) and diodelasers, a multiple quantum well (“MQW”) structure can be formed bydepositing layers of III-V semiconductor with different proportions ofGa and In. Each layer may be on the order of tens of Angstroms thick,i.e., a few atomic layers.

Apparatus of this type can provide a stable and orderly flow of reactivegases over the surface of the carrier and over the surface of the wafer,so that all of the wafers on the carrier, and all regions of each wafer,are exposed to substantially uniform conditions. This, in turn promotesuniform deposition of materials on the wafers. Such uniformity isimportant because even minor differences in the composition andthickness of the layers of material deposited on a wafer can influencethe properties of the resulting devices.

The wafer temperature normally is set to optimize the desired depositionreaction; it is commonly above 400° C. and most typically about700°-1100° C. It is generally desirable to operate equipment of thistype at the highest chamber pressure, lowest rotation speed and lowestgas flow rate which can provide acceptable conditions. Pressures on theorder of 10 to 1000 Torr, and most commonly about 100 to about 750 Torr,are commonly used. Lower flow rates are desirable to minimize waste ofthe expensive, high-purity reactants and also minimize the need forwaste gas treatment. Lower rotation speeds minimize effects such ascentrifugal forces and vibration on the wafers. Moreover, there isnormally a direct relationship between rotation speed and flow rate;under given pressure and wafer temperature conditions, the flow raterequired to maintain stable, orderly flow and uniform reactionconditions increases with rotation rate.

Prior to the present invention, however, the operating conditions whichcould be used were significantly constrained. It would be desirable topermit lower rotation speeds and gas flows, higher operating pressures,or both, while still preserving the stable flow pattern.

SUMMARY OF THE INVENTION

One aspect of the invention provide methods of chemical vapordeposition. A method according to this aspect of the invention desirablyincludes the step of supporting one or more substrates on a carrierwithin a reaction chamber so that surfaces of the substrates faceupwardly within the chamber, while rotating the carrier about a verticalaxis and maintaining the substrates at a substrate temperature of 500°C. or higher. The method desirably also includes the step of directinggases, most preferably gases which include a Group III metal source anda Group V compound, into the chamber from an inlet element disposedabove the substrates. The gases flow downward toward the substrates andoutwardly away from the axis over the surfaces of the substrates andreact to form a deposit such as a III-V semiconductor on the substrates.The gases most preferably are at an inlet temperature above about 75°C., and more preferably above about 100° C. such as about 100° C. toabout 250° C. when introduced into the chamber. Preferably, the walls ofthe chamber are maintained at a temperature within about 50° C. of theinlet temperature.

Preferred methods according to this aspect of the invention can providesignificant improvements in operating range. In particular, thepreferred methods according to this aspect of the invention can operateat lower rotational speeds, lower gas flow rates, and higher pressuresthan similar processes using lower gas inlet temperatures.

A further aspect of the present invention provides a chemical vapordeposition reactor. The reactor according to this aspect of theinvention desirably is a rotating-disc reactor, and desirably includes aflow inlet temperature control mechanism arranged to maintain the flowinlet element of the reactor at an inlet temperature as discussed abovein connection with the method. Most preferably, the reactor alsoincludes a chamber temperature control mechanism arranged to maintainthe walls of the chamber at a wall temperature as discussed above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic view of a reactor according to one embodimentof the invention.

FIG. 2 is a diagrammatic sectional view depicting a component of thereactor shown in FIG. 1.

FIG. 3 is a schematic view of another component of the reactor shown inFIG. 1.

FIGS. 4 and 5 are graphs depicting certain operating conditions.

DETAILED DESCRIPTION

Apparatus according to one embodiment of the invention (FIG. 1) includesa reaction chamber 10 having a central axis 12. In this embodiment, axis12 is substantially vertical as seen in the normal gravitational frameof reference. The interior walls of chamber 10 are generally in the formof surfaces of revolution about axis 12. In a flow region 14 at the topof the chamber, the interior wall 16 is substantially in the form of acylinder having diameter d_(FR) concentric with the axis. A region 18,referred to herein as the “carrier region,” has a cylindrical interiorwall 20 which is also generally in the form of a cylinder concentricwith axis 12 and having diameter d_(CR) larger than d_(FR). The chamberhas a downwardly-facing transition surface 22 at the juncture of theflow region and carrier region. The chamber also has an exit region 24disposed below the carrier region. The chamber walls have passagewaysschematically indicated at 26 for passage of a temperature control fluidwithin the walls as discussed below. Although the walls of the chamberare depicted as unitary elements in FIG. 1, in actual practice the wallsmay be formed from multiple elements. Also, the walls may includemovable sections such as sections defining doors for transferring wafersinto and out of the chamber. Merely by way of example, part or all ofthe interior wall in the carrier region may be defined by a ring-likeshutter which is movable in the axial directions, as shown in U.S. Pat.No. 6,902,623, the disclosure of which is hereby incorporated byreference herein. Unless otherwise indicated, description of the chamberand other elements of the apparatus should be understood as referring tothe configuration of the apparatus in an operative condition usable fordepositing materials.

The apparatus has a wafer carrier drive mechanism, which includes aspindle 28 extending into chamber 10. The spindle is coaxial with axis12 and rotatable about the axis. The wafer carrier drive mechanism alsoincludes a rotary drive mechanism 30 such as an electric motor connectedto the spindle. The apparatus also includes conventional elements suchas bearings and vacuum-tight rotary seals (not shown).

A wafer carrier 32 is mounted on the spindle. The wafer carrier in thisembodiment is a disc-like body formed from a refractory, inert materialsuch as molybdenum, graphite or silicon carbide. The carrier has agenerally planar top surface 34 and pockets 36 formed in the topsurface. The pockets are arranged to hold a plurality of wafers 38 sothat surfaces 40 of the wafers are exposed and are coplanar or nearlycoplanar with the top surface 34 of the carrier. In the operativecondition shown, the wafer carrier is engaged with spindle 28. Thespindle supports the carrier within the carrier region 18 of the chamberwith the top surface 34 and wafer surfaces facing upwardly, toward thetop of the chamber, such surfaces being substantially perpendicular toaxis 12. The diameter d_(C) of carrier 32 is less than the diameterd_(CR) of the carrier region 18, so that the periphery of the carrierand the inner wall 20 of the carrier region define a ring-like gap 41surrounding the carrier and communicating with the exit region 24 of thechamber. For example, in a system with a wafer carrier of about 12.5inches (31.75 cm) diameter d_(C), d_(CR) may be about 15.5 inches (39.4cm). In this embodiment, the interior diameter d_(FR) is approximatelyequal to the diameter d_(C) of the wafer carrier or slightly larger thand_(C). Typically, the wafer carrier is detachably mounted on thespindle, so that the apparatus can be reloaded by removing the wafercarrier from the spindle and replacing it with another carrier bearingnew wafers.

A heater 42, as for example, a resistance heating element, is disposedwithin the reaction chamber for heating the substrate 32 carrier. Anexhaust system 44 is connected to the exit region 24 of the chamber. Theexhaust system is arranged to draw gasses from the interior of thechamber. The exhaust system desirably includes a controllable elementsuch as a variable-speed pump or throttling valves 45 which can beadjusted to maintain a desired pressure within the chamber.

A flow inlet element 46 is mounted to the flow region 14 of the chamberand forms the top wall of the chamber. The flow inlet element isdisposed above the carrier region 18 and above the wafer carrier 32. Theflow inlet element is connected to sources 55 and 56 of the gases usedin the process. The flow inlet element directs streams of the variousgases into the reaction chamber and downwardly toward the wafer carrierand substrates. As further discussed below, the gas streams form asubstantially laminar plug flow within flow region 14 of the chamber.Typically, the flow inlet element is arranged to discharge the gasesover the entire cross-sectional area of the flow region. Stated anotherway, the cross-sectional area of the plug-like laminar flow, viewed in ahorizontal plane perpendicular to axis 12, desirably has a diameterclose to the interior diameter d_(fr) of the flow region. The diameterof the flow as seen in such cross-section desirably is approximatelyequal to or slightly greater than the diameter d_(C) of carrier 32.Typically, the flow inlet element has openings distributed over itsdownwardly-facing bottom surface 48, these openings being connected tothe gas sources. Merely by way of example, the flow inlet element may bearranged as shown in FIG. 2, with first inlets disposed in arraysdistributed over regions such as quadrants 50 of the flow inlet bottomsurface 48 and with second inlets distributed in radially-extending rows52. The first inlets typically are connected to a source 54 (FIG. 1) ofa Group V element such as a hydride, whereas the second inlets typicallyare connected to a source 56 (FIG. 1) of a Group III metal such as ametalorganic. These gas sources normally are arranged to provide theactive reagents in admixture with a carrier gas such as N2 or H2 whichdoes not participate in the deposition reaction. The flow inlet elementalso may have additional openings in its bottom surface for discharge ofa carrier gas without active reagents, supplied by a separate source 55.For example, as disclosed in U.S. Published patent application Ser. No.11/192,483, the disclosure of which is hereby incorporated by reference,the carrier gas may be discharged between streams of Group V and GroupIII elements so as to suppress mixing of these streams and undesiredreactions in the vicinity of the flow inlet element. Also, as disclosedfor example in U.S. Published Patent Application No. 20070134419, thedisclosure of which is also incorporated by reference herein, the flowrates and compositions of the various gas streams may be selected toprovide similar gas density and flow rate in the various gas streams.Flow inlet element 46 has temperature control fluid passages indicatedschematically at 58 for passage of a temperature control fluid.

The foregoing features of the apparatus may be similar to those used inthe reactors sold under the registered trademark TURBODISC by VeecoInstruments, Inc. of Plainview, N.Y., USA.

The temperature control fluid passages 58 of the flow inlet element 46are connected to a flow inlet temperature control mechanism 60. Oneexample of a control mechanism is depicted in FIG. 3. This controlmechanism includes a pump 62 for circulating a fluid, most preferably aliquid such as water, ethylene glycol, a hydrocarbon oil or a syntheticorganic heat transfer liquid such as those sold under the registeredtrademark DOWTHERM, through the temperature control fluid passages 58 ofthe fluid inlet element. The control mechanism also includes one or moresensors 64 for monitoring at least one temperature of the flow inletelement, the gases discharged from the flow inlet element, or thecirculating fluid. The control mechanism desirably also includes astructure such as a radiator 65 arranged to dissipate heat from thecirculating fluid into the environment, and also may include a heatersuch as an electrical resistance heater 66 or other element arranged tosupply additional heat to the circulating fluid. The temperature controlmechanism desirably further includes a control circuit 68 connected tothe one or more sensors 64 and arranged to control operation of theheat-abstracting and heat-applying elements. In the particularembodiment depicted, the control circuit can vary the amount of heatabstracted from the fluid by controlling a bypass valve 70 to divertpart or all of the circulating fluid away from the radiator, and canvary the amount of heat supplied to the fluid by controlling theoperation of an electrical power supply 72 connected to the resistanceheater. Many other arrangements of heat transfer elements can beemployed, and these arrangements need not include a circulating fluid.For example, the flow inlet element can be provided with fins whichdissipate heat directly into the atmosphere and with electrical heatersembedded in its structure. In such an arrangement, the temperature ofthe flow inlet element can be controlled by varying air flow over thefins, by controlling operation of the resistance heaters, or both. It isalso possible to control the temperature of the flow inlet element andof the gases discharged from the flow inlet element by cooling orheating the gasses passing into the flow inlet element. Also, duringoperation, heat is transferred to the flow inlet element from the wafercarrier and wafers. Therefore, it is not essential for the flow inlettemperature control apparatus 60 to include a heat-supplying device suchas resistance heater 66. The inlet temperature control apparatus 60 maybe arranged to control the temperature of different zones of the flowinlet element separately. For example, the temperature control fluidpassages 58 may include separate flow loops for different zone of theflow inlet element, and the temperature control apparatus may includeseparate subsystems associated with each such loop.

The flow inlet element 46 desirably is formed from metals or othermaterials having substantial thermal conductivity, and the gas passages(not shown) within the flow inlet element desirably are in intimatecontact with the flowing fluid in passages 58, so that the temperatureof the gases discharged from the flow inlet element and the temperatureof the flow inlet element itself are close to the temperature of theheat transfer fluid. The flow inlet temperature control apparatus 60 isarranged to maintain the flow inlet element and the gases passing fromthe flow inlet element into the reaction chamber at an inlet temperatureabove about 75° C., more desirably above about 100° C., such as about100° C. to about 250° C., and most typically 100° C. to 250° C.

The apparatus also includes a wall temperature control apparatus 74(FIG. 1). The wall temperature control apparatus may be connected to thetemperature control fluid passages 26 in the walls of chamber 10, andmay include elements similar to those of the inlet temperature controlapparatus 60. The wall temperature control apparatus desirably isarranged to maintain the chamber walls in flow region 14, and desirablyin the carrier region 18 as well, at a wall temperature within theranges discussed above for the inlet temperature. Preferably, the walltemperature is close to the inlet temperature as, for example, withinabout 50° C., and more preferably within about 25° C., of the inlettemperature. The wall temperature control apparatus 74 may includemultiple elements for separately controlling the temperature ofindividual zones of the chamber wall.

In a processing method according to one embodiment of the invention, thegas sources 54-56 are actuated to supply a flow of gases including theGroup III and Group V elements, and typically also including a carriergas, as a laminar, downward plug flow towards the wafer carrier 32 andwafers 38. The gas flow rate typically is about 25 to about 250 standardml per minute per cm² of area cross-sectional area of the plug flow, asseen in a horizontal plane perpendicular to axis 12. Because the area ofthe plug flow as seen in such plane is close to the exposed area of thewafer carrier top surface 34 and wafer top surfaces 40, the gas flowrate computed on the basis of the carrier and wafer area typically isabout the same, i.e., about 25 to about 250 standard ml per minute percm² of area. For example, in a system with a wafer carrier of about 12.5inches (31.75 cm) diameter, the flow rate is commonly about 50-300standard liters per minute, i.e., about 60-400 standard ml/min per cm²of exposed surface area of the wafer carrier and wafer carrier. As usedin this disclosure with reference to a gas, a “standard” liter or mlrefers to a volume of gas at 25° C. (298 and 1 atm absolute pressure.The exhaust system 44 is controlled so as to maintain a desired pressurewithin the reaction chamber as, for example, above about 10 Torr, morepreferably above about 100 Torr, and typically about 250 Torr to about1000 Torr, most commonly about 250 Torr to about 750 Torr. The rotarydrive 30 is actuated to turn the spindle 28 and hence wafer carrier 32around the axis 12 at a desired rotation rate, typically above about 25revolutions per minute, and more typically about 100 to about 1500revolutions per minute. Heater 42 is actuated to maintain the wafercarrier and substrates at a desired substrate temperature, typicallyabove about 400° C., more commonly about 700° C.-1100° C. The substratetemperature normally is selected to optimize the kinetics of thedeposition reaction.

As the wafer carrier 18 is rotating rapidly, the surface of the wafercarrier and the surfaces of the wafers are moving rapidly. The rapidmotion of the wafer carrier and wafers entrains the gases intorotational motion around axis 12, and radial flow away from axis 12, andcauses the gases in the various streams to flow outwardly across the topsurface 34 of the wafer carrier and across the exposed surfaces 40 ofthe wafers within a boundary layer schematically indicated at 76 inFIG. 1. Of course, in actual practice, there is a gradual transitionbetween the generally downstream flow regime denoted by the arrows inthe flow region 14 and the flow in the boundary layer 76. However, theboundary layer can be regarded as the region in which the gases flowsubstantially parallel to the surfaces of the wafers. Under typicaloperating conditions, the thickness T of the boundary layer is about 1cm or so. By contrast, the vertical distance from the downstream face offlow inlet element to the surfaces 40 of the wafers commonly is about5-8 cm.

The rotational motion of the wafer carrier pumps the gases outwardlyaround the peripheral edges of the wafer carrier, and hence the gasespass over the edge of the wafer carrier and downwardly through the gap41 between the wafer carrier and interior wall 20 of the carrier region.The gasses passing through the gap pass to exhaust system 44. A vortex80 typically forms near the interior wall 20 and downwardly-facing wall22. Provided that this vortex remains remote from the wafer carrier andwafers, it does not disrupt the smooth, uniform flow of gases over thewafer surfaces. In general, the vortex tends to increase with therotational speed of the wafer carrier. If the rotational speed of thecarrier is too low, however, recirculation occurs near the central axis12. This recirculation is caused by convection; gases heated by the hotwafer carrier and wafers become less dense and tend to rise.Recirculation of this nature also will disrupt the smooth flow of gasesover the wafer surfaces. Both of these problems tend to become moresevere with increasing pressure within the reactor. The desiredoperating condition, referred to herein as “non-recirculating”operation, occurs when the vortex near interior wall 20 does not extendover the wafer carrier, and when recirculation near the central axis 12does not occur.

These effects are illustrated in FIG. 4. FIG. 4 represents resultsderived by computational flow dynamics for a particular reactoroperating at a gas flow rate, gas composition, substrate temperature andgas inlet temperature, shown on a graph of pressure and rotation rate.Pressure and rotation rate below the solid-line curve in FIG. 4represent non-recirculating operation, whereas pressure and rotationrate above the solid-line curve represent undesirable conditions. Theminimum rotation rate which can be used at a given pressure is governedby convective recirculation. For example, at a pressure of 300 Torr,(solid horizontal line) minimum usable rotation rate is about 260 rpm;below that rate, there is recirculation near the axis due to convection.The maximum rotation rate which can be used at a given pressure islimited by the vortex at the edge of the wafer carrier. At 300 Torr, themaximum rotation rate is about 700 rpm. At higher pressures, the minimumrate increases and the maximum rate decreases, so that at pressure ofabout 480 Torr, the minimum and maximum rates are equal. This means thatthere is no rotation rate where this system, with the given gas flowrate, gas composition, substrate temperature and gas inlet temperaturecan operate in a non-recirculating regime at a pressure of about 480Torr or above.

Although the present invention is not limited by any theory ofoperation, the shape of the curve in FIG. 4 can be understood byconsideration of certain dimensionless numbers and ratios of the same.The Reynolds number Re defined by Formula 1 below provides a measure ofthe significance of forced convection.

$\begin{matrix}{{Re} = \frac{\rho_{mix}v_{mix}d}{\mu_{mix}}} & \left( {{Formula}\mspace{14mu} 1} \right)\end{matrix}$

The Rotational Reynolds number Re_(ω) defined by Formula 2 belowprovides a measure of the significance of forced convection due to therotation of the wafer carrier.

$\begin{matrix}{{Re}_{\omega} = \frac{\rho_{mix}\omega\; d^{2}}{\mu_{mix}}} & \left( {{Formula}\mspace{14mu} 2} \right)\end{matrix}$

The Grashof number Gr defined by Formula 3 below provides a measure ofthe significance of natural convection.

$\begin{matrix}{{Gr} = \frac{g\;\rho_{mix}^{2}{H^{3} \cdot \left( {t_{s} - t_{w}} \right)}}{\mu_{mix}^{2}t_{w}}} & \left( {{Formula}\mspace{20mu} 3} \right)\end{matrix}$

In each of Formulas 1-3:

ρ_(mix), μ_(mix), ν_(mix) represent density, viscosity and velocity ofthe gas mixture, respectively.

ω is the angular velocity of the wafer carrier.

d is the diameter of the wafer carrier.

H is the vertical distance between the flow inlet element and the wafercarrier top surface.

t_(s) is the substrate temperature.

t_(w) is the reactor wall temperature, which is assumed to be equal tothe inlet temperature t_(i).

Criteria for non-recirculating operation are defined by critical valuesof certain dimensionless ratios of Re, Re_(ω) and Gr, as indicated inFormula 4, below. These ratios represent the ratio of the relativestrengths of different forces in the reactor.

$\begin{matrix}{{\frac{Gr}{{Re} \cdot {Re}_{\omega}} \leq C_{1}};{\frac{Gr}{{Re}^{m}} \leq C_{2}};{\frac{{Re}_{\omega}}{{Re}^{n}} \leq C_{3}}} & \left( {{Formula}\mspace{14mu} 4} \right)\end{matrix}$

At very low rotational speeds, the effect of convection is counteractedonly by the plug flow, and is substantially uninfluenced by rotation ofthe wafer carrier. Thus, as long as the inequality for constant C₂ issatisfied, recirculation near the axis due to convection does not occur.This is shown by the horizontal broken line in FIG. 4. At higherrotational speeds, the effect of rotation becomes significant, andoperation without recirculation due to convection occurs if theinequality for constant C₁ is satisfied. This is indicated by theupwardly-sloping broken line in FIG. 4. The vortex outboard of the wafercarrier is enhanced by higher rotation speed but suppressed by greateroutward flow. Operation without the vortex spreading over the edge ofthe carrier occurs if the inequality for constant C₃ is satisfied, asindicated by the curving broken line in FIG. 4.

The effect of gas inlet temperature is shown in FIG. 5. Each curve inFIG. 5 is similar to the solid-line curve of FIG. 4. Here again gas flowrate, gas composition, and substrate temperature are fixed, and thedifferent solid lines represent results computed for different gas inlettemperatures. For each curve, the gas inlet temperature ti and walltemperature tw are equal to one another. Raising the inlet temperaturebroadens the operating range in which non-recirculating conditionsprevail. This effect is particularly pronounced at ti of above about 75°C., and particularly about 100° C. or higher. The curves for ti of 100°C. and 200° C. show non-recirculating operation at substantially higherpressures than the curves for ti of 25° C. and 50° C. Moreover, atoperating pressures where non-recirculating operation can occur for tiof 25° C. or 50° C., the minimum rotational speed is substantiallyreduced at ti of 100° C. or 200° C. For example, at 400 Torr, a minimumrotational speed of almost 400 rpm is required to maintainnon-recirculating operation at ti of 25° C., whereas the minimumrotational speed to maintain non-recirculating operation is only about120 rpm for ti of 200° C. Thus, by increasing the inlet temperature, anddesirably the wall temperature as well, the operating pressure can beincreased, the rotational speed decreased, or both. Moreover, minimumflow rate for stable operation is directly related to rotational speed.As t_(i) increases and rotational speed decreases, the required flowrate of gases through the reactor decreases substantially. These effectswould continue for still higher t_(i). However, with conventionalreagents such as Group III metal alkyls and Group V hydrides, it isordinarily desirable to maintain t_(i) below about 250° C. to limitundesirable side reactions such as formation of solid deposits on theflow inlet element. Where these undesirable reactions can be suppressedin other ways, t_(i) above 250° C. can be used.

In part, these effects can be understood qualitatively. Gasses expandwith increasing temperature. Therefore, for a given gas composition andgiven flow rate (expressed in standard liters per minute), thevolumetric flow rate (expressed in liters per minute) increases withinlet temperature. The higher volumetric flow rate in turn means thatthe velocity of the gas in the downward plug flow is greater. This tendsto counteract the effect of convection. Also, the greater volumetricflow rate means that the speed of the gas moving radially outwardly,away from the axis, is also increased. This tends to keep the vortexaway from the wafer carrier.

Numerous variations and combinations of the features discussed above canbe employed. For example, the size of the reactor and the configurationof the reactor walls can be varied. Also, although the foregoingdiscussion refers to deposition of III-V semiconductors, the inventioncan be employed in chemical vapor deposition of other materials,particularly those which require a high substrate temperature fordeposition and which conventionally employ low gas inlet temperaturesand wall temperatures. Chemical vapor deposition apparatus and processeswhich employ a gas inlet temperature less than the substratetemperature, and a temperature difference ΔT of at least about 200° C.between these temperatures are referred to in this disclosure as “coldwall” apparatus and processes. Typically, ΔT in cold wall apparatus andprocesses is more than 200° C., as, for example, about 400° C. or moreor about 500° C. or more. For example, cold wall apparatus and processesare commonly used in chemical vapor deposition systems in which one ormore of the reactive gasses includes an organic or metalorganiccompound. Certain cold wall deposition apparatus includes a rotatingcarrier. For example, cold wall systems of this type can be used to formsilicon carbide from reactive gases including silane and a lower alkylsuch as propane. Other examples include chemical vapor deposition ofdiamond, diamond-like carbon, nitrides other than the Group III nitridesemiconductors discussed above, and other carbides. The invention can beapplied to these systems as well.

The invention claimed is:
 1. A method of chemical vapor depositioncomprising: (a) supporting one or more substrates on a carrier within areaction chamber so that surfaces of the substrates face upwardly withinthe chamber, while rotating the carrier about a vertical axis andmaintaining the substrates at a substrate temperature of 400° C. orhigher; and (b) directing gases including a Group III metal organiccompound and a Group V hydride into the chamber from an inlet elementdisposed above the substrates so that the Group III metal organiccompound and the Group V hydride flow downward toward the substrates assubstantially separate streams in a flow region extending downwardlyfrom the flow inlet element and then flow outward away from the axisover the surfaces of the substrates in a boundary region between theflow region and the substrates and react to form a III-V compound on thesubstrates, and so that the gases flow in non-recirculating operation,the gases being at an inlet temperature above about 75° C. whenintroduced into the chamber.
 2. A method as claimed in claim 1 furthercomprising maintaining the walls of the chamber at a wall temperaturebetween 75° C. and 250° C.
 3. A method as claimed in claim 1 furthercomprising maintaining the walls of the chamber at a wall temperaturewithin about 50° C. of the inlet temperature.
 4. A method as claimed inclaim 1 wherein the inlet temperature is from 100° C. to 250° C.
 5. Amethod as claimed in claim 1 further comprising the step of maintainingthe pressure within the chamber at about 10 Torr or higher.
 6. A methodas claimed in claim 5 wherein the pressure is about 100 Torr or higher.7. A method as claimed in claim 6 wherein the pressure is about 200 Torrto about 750 Torr.
 8. A method as claimed in claim 1 wherein the carrieris rotated at a rate of about 25 revolutions per minute or greater.
 9. Amethod as claimed in claim 1 wherein the carrier is rotated at a rate ofabout 100 to about 1500 revolutions per minute.
 10. A method as claimedin claim 1 wherein the step of directing gases is performed so that thegases flow in a laminar plug flow downwardly, parallel to the axis, fromthe inlet element.
 11. A method as claimed in claim 10 wherein thelaminar plug flow has a cross-sectional area in a horizontal planeapproximately equal to or larger than an area of the carrier andsubstrates in a horizontal plane.
 12. A method as claimed in claim 10wherein the laminar plug flow provides about 25 to about 250 standard mlper minute per cm² of area of the carrier and substrates.
 13. A methodas claimed in claim 1 further comprising exhausting gases from thechamber below the carrier, so that gases passing outwardly away from theaxis move generally downwardly between an outer edge of the carrier andthe wall of the chamber.
 14. A method as claimed in claim 1 wherein thegases include one or more carrier gases.
 15. A method as claimed inclaim 1 wherein the inlet temperature is less than the substratetemperature, such that there is a temperature difference of at leastabout 200° C. between the inlet temperature and the substratetemperature.
 16. A method as claimed in claim 15 wherein the temperaturedifference is at least about 400° C.
 17. A method as claimed in claim 15wherein the gases include one or more compounds selected from the groupconsisting of organic and metalorganic compounds.
 18. A method asclaimed in claim 15 further comprising maintaining the walls of thechamber at a wall temperature within about 50° C. of the inlettemperature.
 19. A method as claimed in claim 1 wherein the substratetemperature is from 700° to 1100° C., the chamber is maintained at apressure of about 100 Torr or higher and the carrier is rotated at arate of about 100 to about 1500 revolutions per minute.
 20. A method asclaimed in claim 19 wherein the step of directing gases is performed sothat the gases flow in a laminar plug flow downwardly, parallel to theaxis in the flow region, the laminar plug flow having a cross-sectionalarea in a horizontal plane approximately equal to or larger than an areaof the carrier and substrates in a horizontal plane, and wherein thelaminar plug flow provides about 25 to about 400 standard ml per minuteper cm² of area of the carrier and substrates.
 21. A method as claimedin claim 20 wherein the inlet temperature is from 100° C. to 250° C. andthe pressure is from 250 Torr to 1000 Torr.
 22. A method as claimed inclaim 1 wherein the gasses consist essentially of the Group III metalorganic compound and the group V hydride, with or without one or morecarrier gasses.
 23. A method as claimed in claim 1 wherein the flowinlet element is spaced apart from the carrier and substrates by 5 cm to8 cm.
 24. A method as claimed in claim 1 wherein the Group III metalorganic compound includes a gallium metal organic compound, the Group Vhydride includes ammonia and the III-V compound includes galliumnitride.
 25. A method as claimed in claim 1 wherein the Group III metalorganic compound includes a gallium metal alkyl, the Group V hydrideincludes ammonia and the III-V compound includes gallium nitride.
 26. Amethod as claimed in claim 25 wherein the inlet temperature is from 100°C. to 250° C.
 27. A method as claimed in claim 25 wherein the inlettemperature is 200° C.